Ground-state complex formation of perylene with pyromellitic dianhydride studied by static fluorescence quenching

The association of complex formation with static quenching in CT systems was investigated. Evaluation of the data made evident that the inner filter effect must be allowed for. Time-resolved and temperature-dependent stationary measurements of fluorescence led to the separation of dynamic and static quenching components. The static quenching constant is discussed with respect to the equilibrium constant of complex formation determined by absorption spectroscopy.     

β-Lactam Derivatives as Enzyme Inhibitors: Peptidic Derivatives of ( RS )-2-Oxo-4-phenylazetidine-1-alkanoic Acids

4-Phenylazetidine-2-one was transformed into 4-phenylazetidine-1-alkanoic acids, which were reacted in the presence of diphenylphosphoroazidate with amino acid esters and dipeptide esters yielding β-lactam peptides with different spacers between the lactam ring and the peptide moiety. All structures were established by elementary analyses, HPLC, optical rotation, and spectroscopic data and all new compounds were tested as inhibitors of PPE using standard procedures. Four compounds exhibited a weak activity compared with the standard inhibitor trifluoroacetyl-l-val-l-tyr-l-val.     

Synthesis of (-)-2s,3s, 11s,12r-2,3,11,12-tetraphenyl[18]crown-6

The synthesis of ( - ) 2S,3S,11S,12R-2, 3,11,12-tetraphenyl [18]-crown-6 from (-)-1S,2S-hydrobenzoin and meso-hydrobenzoin is described. Chemical shifts and vicinal coupling constants of the benzylic protons in the 2 S, 3 S and 11 S,12 R substructures in the free ligands and in complexes with KSCN and 1-phenylethylammonium bromides and a brief discussion of the related conformational changes are also presented. A detailed procedure for the resolution of racemic hydrobenzoin is given.     

Diastereoselective cascade synthesis of azabicyclo[3.1.0]hexanes from acyclic precursors

The diastereoselective synthesis of azabicyclo[3.1.0]hexanes bearing different substituents on all positions of the cyclopropane ring has been achieved in moderate to good yields.     

Total synthesis of the ramoplanin A2 and ramoplanose aglycon

A convergent total synthesis of the ramoplanin A2 and ramoplanose aglycon is disclosed. Three key subunits composed of residues 3-9 (heptapeptide 15), pentadepsipeptide 26, and pentapeptide 34 (residues 10-14) were prepared, sequentially coupled, and cyclized to provide the 49-membered depsipeptide core of the aglycon. Key to the preparation of the pentadepsipeptide 26 incorporating the backbone ester was the asymmetric synthesis of an orthogonally protected L-threo-beta-hydroxyasparagine and the development of effective and near-racemization free conditions for esterification of its hindered alcohol (EDCI, DMAP, 0 degrees C). The coupling sites were chosen to maximize the convergency of the synthesis including that of the three subunits, to prevent late stage racemization of carboxylate-activated phenylglycine-derived residues, and to enlist beta-sheet preorganization of an acyclic macrocyclization substrate for 49-membered ring closure. As such, macrocyclization at the chosen Phe(9)-D-Orn(10) site may benefit from both beta-sheet preorganization as well as closure at a D-amine terminus. Deliberate late stage incorporation of the subunit bearing the labile depsipeptide ester and a final stage Asn(1) side chain introduction provides future access to analogues of the aglycons which themselves are reported to be equally potent or more potent than the natural products in antimicrobial assays.     

Investigation of nucleation processes under the influence of magnetic fields

The present work demonstrates the possibilities and the limits of the in situ electrochemical scanning tunneling microscopy for investigation of nucleation processes in magnetic fields on the examples of Cu and Co electrodeposition onto Au(111) electrodes from sulfate electrolytes with pH 3. Cyclic voltammograms of Cu in the underpotential range (UPD) exhibit no significant change in the cathodic and anodic peaks recorded in magnetic fields parallel to the surface. In magnetic fields of a permanent magnet, the reconstruction of Au has been annihilated during UPD of Cu. In the overpotential range, the dissolution of Cu is inhibited. This triggers the formation of a Cu–Au surface alloy. The UPD deposition of Co onto Au(111) could be proven without magnetic field, which leads to the formation of two monolayers. The nucleation in an applied field could not be observed due to higher induced fluctuations and microconvective effects. Contribution to special issue “Magnetic field effects in Electrochemistry”.     

Numerische Ermittlung quasikonformer Abbildungen mit finiten Elementen

Summary In this note we consider so called p-analytic mappings of simply or doubly connected domains on rectangles or circular rings. Real and imaginary parts of the mappings can be described by minimal-principles. By minimizing the corresponding functionals in a class of linear or bilinear finite elements we obtain an approximation of the mapping and also upper and lower bounds for the p-module of a domain with polygonal boundary. Error bounds are given for smooth and for piecewise constant functionsp. We present numerical experiments.

     

Determination of physiological noble metals in human urine using liquid-liquid extraction and Zeeman electrothermal atomic absorption spectrometry

An extremely sensitive, reliable and simple procedure is described for the determination of physiological palladium, platinum and gold in human urine. The urine samples were adjusted to pH 4 (Pd, Au) or pH 5 (Pt), followed by conversion of the analytes to their pyrrolidinedithiocarbamate complexes. These complexes were separated from the matrix by liquid-liquid extraction into 4-methyl-2-pentanone resulting in a 25-fold enrichment. Determination was by electrothermal atomic absorption spectrometry (ET-AAS) using longitudinal inverse alternating current Zeeman-effect background correction. The limits of detection calculated from three standard deviations of the blank values were 20 ng l⁻¹ for Pd and Au and 70 ng l⁻¹ Pt. Within-day precision (n = 10, 5 μg l⁻¹) ranged 5.2%–7.7%. The procedure is successfully applied to determine urinary palladium, platinum and gold in nine unexposed persons. Palladium levels in urine ranged < 20–80 ng l⁻¹ (arithmetical MEAN=38.7 ng l⁻¹), while gold levels ranged < 20–130 ng l⁻¹ (36.0 ng l⁻¹). Physiological platinum levels in urine were all < 70 ng l⁻¹. The accuracy of the procedure was checked by analyzing a series of urine samples by a second independent method (magnetic sector field inductively-coupled plasma-mass spectrometry) in combination with UV photolysis.     

Ultraviolet B Wavelength Dependence for the Regulation of Two Major Matrix-Metalloproteinases and Their Inhibitor TIMP-1 in Human Dermal Fibroblasts

Abstract— The wavelength dependence for the regulation of two major matrix-metalloproteinases, interstitial collagenase (MMP-1) and stromelysin-1 (MMP-3), and their major inhibitor, tissue inhibitor of metalloproteinases (TIMP-1), was studied in human dermal fibroblasts in vitro. Monochromatic irradiation at 302, 307, 312 and 317 nm with intensities ranging from 20 to 300 J/m² increased MMP-1 and MMP-3 mRNA steady-state levels and the secretion of the corresponding proteins up to 4.4-fold, whereas almost no increase was observed at wavelengths <290 nm. In contrast, the synthesis of TIMP-1 increased only marginally. This unbalance may contribute to the severe connective tissue damage related to photoaging of the skin. The wavelengths responsible for MMP-1 and MMP-3 induction reported here are distinct from the absorption spectrum of DNA and are different from results previously reported in the literature. Importantly, they overlap with wavelengths whose intensity is predicted to increase on the earth's surface upon ozone depletion. Intensities and particular wavelengths used in our studies in vitro can be absorbed readily by fibroblasts within the skin in vivo and, thus, are relevant for risk assessment and development of protective agents.